Preparation and characterisation of thermoresponsive poly[(N-isopropylacrylamide-co-acrylamide-co-(hydroxyethyl acrylate)] microspheres as a matrix for the pulsed release of drugs

Despite the large number of publications and patents concerning pH/thermoresponsive polymers, few data are available concerning the preparation of thermoresponsive cross-linked microspheres from preformed polymers. Therefore, N-isopropylacrylamide-co-acrylamide-co-(2-hydroxyethyl acrylate) copolymers were obtained as a new thermoresponsive material with a lower critical solution temperature (LCST) around 36 degrees C, in phosphate buffer at pH 7.4, and with a cross-linkable OH group in their structure. The LCST value was determined both by UV spectroscopy and microcalorimetric analysis. These copolymers were solubilised in acidified aqueous solution below their LCST, dispersed in mineral oil, and transformed into stable microspheres by cross-linking with glutaraldehyde. The thermoresponsive microspheres were characterised by optical and scanning electron microscopy, degree of swelling, and water retention. The pore dimensions of the microspheres and the retention volumes of some drugs and typical compounds were evaluated at different temperatures by liquid chromatography. Indomethacin, as a model drug, was included in the microspheres by the solvent evaporation method. Finally, the influence of temperature and of temperature cycling on drug release was investigated.     

Photometrische Bestimmung von Kohlenmonoxyd in der Luft

Zusammenfassung Es wird ein photometrisches Verfahren der CO-Bestimmung beschrieben, das auf der Absorption des Gases in einer alkalischen Lösung der Silberverbindung der p-Sulfamidbenzoesäure beruht. Die Silberverbindung wird zu metallischem Silber reduziert, das in kolloider Verteilung bleibt. Die Extinktion dieses Silbersols wird gemessen. Sie ist unter den Bedingungen der Arbeitsvorschrift im Bereich von 0,001–0,5% CO der Konzentration des Kohlenmonoxyds proportional. Bei Wellenlängen unterhalb 500 m nimmt die Extinktion stark zu. Die Messungen werden deshalb zweckmäßig im kurzwelligen Licht durchgeführt. Mit Zeiss-Filter S 42 wird z. B. nahezu die doppelte Meßempfindlichkeit erreicht wie mit Filter S 50. Die Durchführung der CO-Bestimmung wird genau beschrieben.     

Model-based sensitivity analysis of a fluidised-bed bioreactor for mercury uptake by immobilised Pseudomonas putida cells

A model-based sensitivity analysis was performed in order to evaluate the importance of the individual operating parameters of a three-phase fluidised-bed biological reactor used for removing mercury ions from wastewater. The parameters analysed involve the immobilised biomass load (bacteria P. putida) on alginate beads, particle size, inlet flow-rate, mercury ion loads in the fed wastewater, and the solid fraction in the reactor. Predictions were generated by using pseudo-first-order, Michaelis-Menten, or pseudo-Haldane kinetic models. The results highlight the major influence of the biomass/solid load and of the liquid residence time on the reactor efficiency. Also, the resultant significant differences in the model predictions underline the importance of using a more accurate kinetic model for process design and control purposes.     

The Vapor-Liquid Polycondensation of Cyclohexylphosphoric Dichloride with Hydroquinone

The vapor-liquid polycondensation of cyclohexylphosphoric dichloride with hydroquinone was investigated. The influence of the temperature, reaction time, base concentration, and molar ratio of reagents on the yield, inherent viscosity, and molecular weight of the obtained polymer was studied. Second order, central, composite, rotatable experimental design was used in order to carry out this work and to mark limits of the experimental field for optimal yields and high inherent viscosities.     

Homogenization heat treatment and segregation analysis of equiaxed CMSX-4 superalloy for gas turbine components

Journal of Thermal Analysis and Calorimetry - Two new zinc(II) coordination compounds have been synthesized by the reaction of diazine-ring containing Schiff bases di(2-pyridyl) ketone...     

Derivatives of Some 2-Chloroethylphosphonic Acid Esters,with Plant Growth Regulating Activity

Abstract

A method for the synthesis of esters of 2-(dimethylsulfonium)ethylphos-phonic acid and the results of some trials showing the plant growth regulating activity of these compounds are presented. For the synthesis of the mentioned compounds, dimethyl sulphide is reacted with 2-chloroethylphosphonic acid esters; these esters are obtained through the complex[1] of AlCl₃, PCl₃ and 1,2-dichloroethan (1). Using the optimum reaction conditions, very good yields were obtained (96–99%). This complex is reacted with different alcohols to give 2-chloroethylphosphonic acid esters (2) (R?Me, Et, Pr, i-Pr, Bu, i-Bu, Pe). Using the optimum reaction conditions, in the case of methanol the maximum obtained yield was 50%. In the case of the other alcohols, the obtained yields were between 76 and 83%. An exception is i-propanol. whose ester was obtained with low yields and the reaction parameters modification have little influence on the yield. The reaction of the esters with dimethyl sulphide gives, in good yields (between 69 and 79%). esters of 2-(dimethylsulfonium)ethylphosphonic acid (3). substances with plant growth regulating activity.     

Explanation of Anomalous Gas-Chromatographic (Gc) Behaviour in a Homologous Series of 2-Chloroethyl Phosphonic Acid Dialkyl Esters

Abstract

The study of GC separation of 2-chloroethylphosphonic acid di-n-alkyl (1–5 C atoms) esters (synthesised by us) on silicone stationary phases (OV-1, OV-17, OV-225) revealed a deviation from the expected linear dependence of retention indexes (RI) versus the number of C atoms of the alkyl chain: the first member of the series presents stronger retention than one can expect. This anomalous behaviour was observed especially on polar stationary phase (OV-225, see Figure l), and was emphasised with the increase of the column temperature. In an attempt to rationalise the above mentioned facts, we tried to relate the RI values to a global polarity parameter: the dipole moment, μ. The μ values for ClC₂H₄P(O)(OR)₂ were calculated by a method described in [1] (tested by comparing the calculated μ values with experimental ones for alkyl phosphonic acid dialkylesters), using molecular mechanics (COSMIC package) in the search of the conformational space, AM1 method (MOPAC 6.0) for the μ values of the conformers, and Boltzmann distribution for the global value (see Table I). At low temperature, the μ values are not related to the Kovats indexes. Those calculated at 200°C (column temperature range) demonstrate that, indeed, only in the case of the methyl derivative, the temperature rising led to a higher μ (enhanced population of the more polar conformers: ac position for the C-Ethyl group - ac for the Cl, μ ≈ 27 D, or ±ap for one R, μ ≈ 3.8 ÷ 4.3 D). It can be concluded that dipole-dipole forces contribute to the separation process of the first members of the series.     

Synthesis of Mixed Alkylphosphites and Alkylphosphates

Some mixed phosphites having two different alkyl chain were obtained as forerunners for mixed phosphates Mixed dialkyl phosphates were obtained in good yields (40-80%) by phase transfer catalysis in liquid-liquid sistem, starting from different dialkyl phosphites and aliphatic alcohols. The reaction conditions were optimized in order to obtain good yields in phosphites and phosphates respectively. Compounds were analyzed by IR, P 31 -NMR.     

Thermostable Trioxane-Dioxolane Copolymers Obtained with Boron Trifluoride: Acrylonitrile Complex as Initiator

Trioxane was copolymerized with small amounts of dioxolane in benzene in the presence of a boron trifluoride:a crylonitrile complex as initiator. The kinetics of reactions was expressed in terms of topoenergetic principles. The copolymerizations had no induction periods and the maximum reaction rate was found proportional to the square of both the initiator and monomers concentrations. A zwitterionic mechanism is suggested for initiation. The activation energy for the system with 5% dioxolane was determined as 18.3 kcal/mol. The melting behavior of the copolymers is briefly discussed as a function of the dioxolane initial content, and is indicative of the amorphous-crystalline coupling phenomenon. The copolymers with ～ 5% dioxolane are thermostable in air up to 250%deg; and are recommended for practical purposes.